AU630819B2

AU630819B2 - Benzyl ketones and fungicides containing them

Info

Publication number: AU630819B2
Application number: AU79295/91A
Authority: AU
Inventors: Eberhard Ammermann; Reinhard Doetzer; Gisela Lorenz; Franz Roehl; Hubert Sauter; Horst Wingert
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1990-06-27
Filing date: 1991-06-26
Publication date: 1992-11-05
Anticipated expiration: 2011-06-26
Also published as: ATE121071T1; HU912140D0; CA2045044A1; EP0463513A2; GR3015774T3; DE59105144D1; NZ238713A; IL98628A0; JPH04230234A; DE4020397A1; US5147892A; EP0463513B1; DK0463513T3; KR920000688A; ZA914916B; EP0463513A3; ES2071167T3; HU208665B; HUT58034A; AU7929591A

Abstract

Benzyl ketones of the formula <IMAGE> where X is CH or N, Y is O or NR4, R1, R2 are H or alkyl, R3 is halogen, cyano, nitro, alkyl, cycloalkyl, alkoxy, haloalkyl, arylalkyl, arylalkoxy, aryloxy or aryl, and the aryl groups in turn may be substituted, R4 is OH, alkoxy or arylalkoxy and R5 is H, methyl, halogen or methoxy, and fungicides containing these compounds.

Description

U Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class I nt. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: P. tority Related Art 11(ame of Applicant: BASF AKTIIENGESELLSCHAFT Address of Applicant: D-6700 Ludwigshafen, Federal Republic of Germany Actual Inventor~: HORST WINGERT, HUBERT SAUTER, FRANZ ROEHL, REINHARD EX)ETZER, GISELA LORENZ, EBERHIARD AME1R1ANN hddres, for Service: WATERMIARK PATENT TRADEMIARK ATTORNEYS.

LOCKED BAG NO. 5, H[AN.VTHORN, 'VICTORIA 3122, AU~STRALIA Complete Specification for the !nventirn entitled: BENZYL KEIDNES AND FUNGICIDES CONTAINING THEMV The followg statement is a full description of this invention, including the best method of performing it known to us i i_ i~ O.Z. 0050/41690 Benzyl ketones and funcicides containing them The present invention relates to benzyl ketones, fungicides which contain these compounds and methods for controlling fungi with these compounds.

It is known that 2-(phenoxymethyl)-phenylglyoxylic acid methyl ester 0-methyloxime can be used as a fungicide (European Patent 253,213). However, the fungicidal action of the compound is unsatisfactory.

It is an object of the present invention to provide active ingredients and fungicides having a better action.

We have found that this object is achieved and that benzyl ketones of the general formula I 0n C- C" 0 O C O0

R

Y

I I o C C X-0R2 .1 where X is CH or N, Y is 0 or NR 4

R

1 and R 2 are each H or

C

1

-C

4 -alkyl, R 3 is H, halogen, cyano, nitro, Ci-C 6 -alkyl, j a

C

3 -C-cycloalkyl, Ci-C-alkoxy, halo-C 1 or -C 2 -alkyl, aryl-

SC

1 or -C 2 -alkyl, aryl-Ci- or -C,-alkoxy, aryloxy or aryl, and the aryl groups in turn may be substituted by from one to three of the radicals halogen, cyano, nitro, Co C C-alkyl, C 1 -C-alkoxy or i.alo-C,- or -C 2 -alkyl, R 4 is OH, a C-C 6 -alkoxy or aryl-CI- or -C 2 -alkoxy and R 5 is H, methyl, 0 0 0halogen or methoxy, have a better fungicidal action than the known active ingredients.

Preferred benzyl ketones of the general structural formula I i 2 O.Z. 0050/41690

R

Y

C' R ()3 0 C C X-OR2 0 R1 II are those in which X is CH or N, Y is 0 or NR 4

R

1 and R 2 j are each H or C 1

-C

4 -alkyl (eg. methyl, ethyl, n- or isopropyl or iso-, sec- or tert-butyl), R is H, halogen (eg. F, Cl, Br or nitro, cyano, Cl-C 6 -alkyl (eg. methyl, ethyl, n- or isopropyl, iso-, sec- or tert-butyl, n-pentyl or n-hexyl), C 3

-C

6 -cycloalkyl (eg.

j cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), Si C 1 -C-alkoxy (eg. methoxy, ethoxy, n- or isopropoxy, n-, iso-, sec- or tert-butoxy, pentyloxy or hexyloxy), halo- C- or -C 2 -alkyl (eg. trifluoromethyl, trichloromethyl or pentafluoroethyl), aryl-C l or -C 2 -alkyl (eg. benzyl or phenylethyl), aryl-Cl- or -Cz-alkoxy (eg. benzyloxy or phenylethoxy), aryloxy (eg. phenoxy) or aryl (eg. phenyl), and the aryl group in turn may be substituted by from one to three of the radicals halogen, cyano, nitro, Ci-C 6 alkyl, Cl-C.-alkoxy or halo-C i or -C 2 -alkyl, R is OH, Ci-C 6 -alkoxy or aryl-Cl- or -Cz-.alkoxy and R 5 is hydrogen.

Compounds of the general structural formula I where X is CH or N, Y is O, R I and R z are each methyl, R 3 has the abovementioned meanings and R 5 is hydrogen are particularly preferred.

SBecause of the C=X double bond, the novel com- J pounds of the general formula I may occur both as E and as Z isomers, which can be separated in a conventional manner. Both the individual isomeric compounds and mixtures thereof form subjects of the invention and can be used as fungicides.

The novel benzyl ketones I where Y is O are obtained, for example, by converting a benzyl halide of 3 O.Z. 0050/41690 the general formula II in a conventional manner (cf.

Houben-Weyl, Vol. 13/2 a, page 553 et seq.; P. Knochel, J. Org. Chem. 53 (1988), 2390) into an organo-zinc-copper compound of the general formula III and reacting the latter with a carbonyl halide of the general formula IV Berk, P. Knochel and M.C.P. Yeh, J. Org. Chem. 53 (1988), 5789).

R3 ual u(CN)Zn Hal I 2. CuCN T -X OR2 X-OR 2

OR

1 OR1 II III X, R 1

R

2 and R 3 have the same meanings as in formula I and Y is Hal in formulae II and III is halogen, preferably bromine; Hal in formula IV is halogen, prefer-, ably chlorine.

The benzyl halides II are reacted with activated zinc, as a rule from -5 to 10°C, preferably at 0 C Knochel, M.C.P. Yeh, S.C. Berk and J. Talbert, J.

Org. C-em. 53 (1988), 2390). The reaction to give the I organo-copper-zinc compound is then carried out using the tetrahydrofuran-soluble CuCN-2LiCl complex, at from to The reaction with the carbonyl halides IV is carried out, for example, in an inert, anhydrous solvent, eg. tetrahydrofuran, at from -70 to Alternatively, the compounds of the general structural formula I where Y is 0 can also be prepared by reacting a benzyl halide of the formula II with a carbonyl halide of the formula IV in the presence of zinc and a transition metal catalyst, eg. Pd(Ph 3

P)

4 PdCl 2 Pd(Ph 3

P)

2 Cl2, Pd(PhCN) 2 C1 2 Pd(OAc) 2 or Ni(PPh 3 2 zC 2 in an inert solvent, eg. tetrahydrofuran, toluene or preferably dimethoxyethane, at from -10 to +100°C (cf. T. Fujisawa

A

4 O.Z. 0050/41690 et al., Chem. Lett. (1981), 1135), where Ph is phenyl.

+R3 Hal% Zn Transition metal catalyst Because of the C=X double bond, the starting compounds II may be in the form of E/Z isomer mixtures or pure E or Z isomers, so that the corresponding subsequent products, including the benzyl ketones I, are obtained either as E/Z isomer mixtures or as E or Z isomers. The invention relates both to the individual isomeric compounds and to mixtures thereof.

The preparation of the starting compounds II S 10 (X CH) is described in European Patent 226,917 and that Sof the compounds II (X N) is described in European SPatent 354,571.

The carbonyl halides of the general formula IV S(where R 3 has the abovementioned meanings) are either known or can be prepared by processes similar to known processes. Appropriate preparation methods are described in, for example, Houben-Weyl, Methoden der organischen Chemie, Vol. E5, page 587.

SThe compounds of the general formula I where Y is a 20 NR 4 can be prepared from the corresponding compounds of the formula I where Y is 0 by reacting the latter in a S° conventional manner with an amine of the general structure NH 2

R

4 where R 4 has the meanings stated in claim 1 2 5 (cf. Houben-Weyl, Methoden der organischen Chemie, Volume X/4, page 1).

The Examples which follow illustrate the preparation of the benzyl ketones.

I

i i 5 O.Z. 0050/41690 i i i i i i: i i "D i j EXAMPLE 1 Preparation of methyl 2-(2-chlorophenylcarbonylmethyl)phenyl-B-methoxyacrylate (compound 5, Table 2) 700 mg of 1,2-dibromoethane are added to 2.3 g of zinc powder in 20 ml of THF (tetrahydrofuran). Refluxing is carried out until evolution of gas has ended, the mixture is allowed to cool to room temperature (20 0 C) and 0.2 ml of trimethylchlorosilane is added. A solution of g (35 mmol) of methyl a-(2-bromomethylphenyl)-Bmethoxyacrylate in 40 ml of THF is added dropwise to this solution at 0 C and stirring is continued for 3 hours at 5°C. Thereafter, the mixture is cooled to -78°C and a solution of 3.2 g of copper cyanide and 3 g of lithium chloride in 40 ml of THF is added. The mixture is 15 allowed to thaw for 5 minutes at -20°C and is again cooled to -78 0 C, and a solution of 6.1 g oi 2-chlorobenzoyl chloride in 20 ml of THF is added dropwise. Stirring is carried out overnight at room temperature. The reaction mixture is poured onto water and extracted with ethyl acetate, and the organic phase is dried and evaporated down. Chromatography over silica gel using hexane/ethyl acetate gives 4.1 g of compound No. 5 (Table 2) as a colorless solid of melting point 70-75 0 C. Yield: EXAMPLE 2 25 Methyl 2-(phenylcarbonylmethyl)-phenyl-B-methoxyacrylate (compound 1, Table 2) A solution of 5 g (17.5 mmol) of methyl a-(2-bromomethylphenyl)-B-methoxyacrylate and 2.5 g (17.8 mmol) of benzoyl chloride in 50 ml of dimethoxyethane is added dropwise to 2.3 g (0.035 mol) of zinc powder and 600 mg (0.9 mmol) of Pd(Ph 3

P)

2 C1 2 under nitrogen and the mixture is then h ated at 50 C for minutes. Water is added, the mixture is extracted with ethyl acetate and the organic phase is dried and evaporated down. The residue is chromatographed over silica gel using hexane/ethyl acetate. 1.6 g of compound No. 1 (Table 1) are obtained as a pale yellow solid of melting tn o 0 ZP~ o 0 6 0.Z. 0050/41690 point 97-99 0 C. Yield: 29%.

The compounds given in the tables below may be prepared analogously.

a a CC 900280 0.z. 0050/41690 Table 1 0 C \C X-0R 2

OR

1

R

3

R

No. X y Phys. data

IR)

1 2 3 4 6 7 8 9 715 11 12 13 14 16 0 0 0 0 0 0

NR

4 NR 4

NR

4

NR

4

NR

4 0 0

NR

4

NR

4

NR,

4

H

CH

3

C

2

H

5 n-C 3 H5

CH

3 CH3

CR

3

CH

3

CH

3

CH

3

CH

3 C 2

H

5 n-C 3

H

7 CR3

CH

3 CR3

CH

3

H

CH

3

CH

3 C 2

H

n-C 3

CR

3

CH

3

CR

3

C-R

3

CR

3

CR

3

CR

3

CR

3

CR

3

CH

3

OH

OCH3 0C 2

H

O (n-C 3

H

7 OCH2C6H5

OCR

3 0C 2

OCH

2

C

6 4 2.

m 900280 o.z. 0050/41690 Table 2 MeO2 C OM~eR3 No. R Phys. data (inn. IR')

I

1 2 3 4 6 7 8 9 11 12 13 14 C 15 16 17 18 19 21 22 C 23 24 26 27 28 29 31 32 33 34

H

2-F 3-F 4-F 2-Cl 3-Cl 4-Cl 2-Br 3-Br 4-Br 2-1 3-1 4-1 2-CN 3-CN 4-CN 2-NO 2 3-NO 2 4-NO 2 2-Methy I 3-MethylI 4-MethylI 2-EthylI 3-EthylI 4-Ethyl 2-n-Propy I 3-n-Propy 1 4-n-Propy I 2-iso-P ropy 1 3-iso-Propyl 4-i so-Propyl 2-n-Buty 1 3-n-Buty 1 4-n-Buty 1 2-iso-Butyl 97- 990C 70- 75 0

C

93-108 0

C

111-117 0

C

76- 82 0

C

67- 71 0

C

88- 91 0

C

900280 9 0.Z. 05/19 Table 2 (contd.) No. R 3 Phys. data (nip., IR) 36 3-iso-Butyl 37 4-iso-Butyl 38 2-sec--Butyl 39 3-sec-Butyl 4-sec-Butyl 41 2-tert.-Butyl 42 3-tert.-Buty1 43 4-tert.--Butyl 44 2-n-Pentyl 3-n-Pentyl 46 4-n-Pentyl 47 2-n-Hexyl 48 3-n-Hexyl 49 4-n-Hexyl 2-Cyclopropyl 51 3-Cycilopropyl 52 4-Cyclopropyl 53 2-Cyclohexyl 54 3-Cyclohexyl 4-Cyclohexyl 56 2-Methoxy 57 3-Methoxy 58 4-Methoxy 59 2-Ethoxy 3-Ethoxy 61 4-Ethoxy 62 2-n-Propoxy 63 3-n-Propoxy 64 4-n-Propoxy 2-iso-Propoxy 66 3-iso-Propoxy 67 4-iso-Propoxy 68 2-tert.-Butoxy 69 3-tert.-Butoxy 4-tert.-Butoxy 71 2-CF3 72 3-CF 3 73 4-CF3 ~m 900280 o.z. 0050/41690 Table 2 (contd.) No.

R

3 Phys. data

IR)

I

2-Benzy I 3-Benzyl 4-Benzyl 2-f 4-Chl1orobenzy 1) 2-[4-Methoxy-benZyl J 4-Methoxy-3-benzyl 2-f 2-Pheny lethyl J 3-li2-Phenylethy I] 4-[2-Phenylethyl] 2-Benzyl1oxy 3-Benzyloxy 4-Benzyloxy 2-Ph en oxy 3-Phenoxy 4 00 1706,1683,1631,1580,1489,1435, 1250,1128 88 89 91 92 93 94 a 96 0~ 97 98 0 99 100 101 102 103 104 105 106 107 108 109 4-Phenoxy 2-Ph eny I 3-Phenyl 4-Ph eny 1 2-[3-Br, 4-Me-phenylJ 2-[4-Me-phenyl] 4-li4-Et-pheny 11 4-l4-n-Propyl-pheny 1) 4-f 4-Bromophenoxyl 2,3-F2 2,4-F 2 2,5-F2 2,6-F2 3,4-F 2 3, 5-F 2 2, 3-Cl 2 2,4-Cl 2 2,5-Cl 2 2, 6-CI 2 3,4-Cl 2 3,5-Cl 2 2,5-Br 2 900280 11 0.z. 0050/41690 Table 2 (contd.) No. R 3 Phys. data

IR)

110 2-Cl, 4-Br i11 2-Cl, 112 2-F, 6-CI 113 3-Cl, 6-Br 114 4-F, 115 2-F, 4-Cl 116 4-F, 117 2-F, 3-Cl 118 4-F, 2-Cl 119 2-Cl, 6-Me 120 3-Cl, 2-Me 121 3-Cl, 4-Me 122 3-Cl, 6-Me 123 4-Cl, 124 4-Cl, 6-Me 125 3-F, 4-Me I 126 3-F, 6-Me, 127 2-Cl, 128 2,6-Cl 2 3-Me 129 3-CN, 4-Me 130 ?,3-Me292- 97 0

C

131 2,4-Me2 132 2,5-Me2 133 2,6-Me2 134 3,4-Me2 135 3,5-Me2 136 2,4,6-Me3 137 2,6-(CF 3 )2 138 2,4-(CF 3 )2 139 3,5-(CF 3 )2 140 2-F, 4-CF 3 141 3-F, 5-CF 3 142 4-F, 3-CF 3 143 2-Cl, 4-CF3 144 2,3-(OCH3)2 145 2,4-(OCH3)2 146 2,5-(OCH3)2 147 2,6-(OCH3)2 148 3,4-(OCH3)2 900280 12 0.Z. 0050/41690 Table 2 (contd.) No. R3Phys. data (nip., IR) 149 3,5-(OCH 3 2 150 2-OCH 3 3-CH 3 151 2-OCH3, 4-CH 3 152 2-OCH3, 5--CH 3 153 2-OCH 3 4-Cl 154 2-OCH3, 155 2-OCH 3 3,5-Cl 2 156 2-OCH3, 3,6-Cl 2 157 2,6-1--H 3 2 3-CI 158 4-OCH 3 2-Cl 159 4-OCH 3 3-Cl 160 4-OCH3, 3-F 161 4-OCH 3 2-CH3 Me =Methyl 900280 13 0.z. 0050/41690 Table 3 a 0 3 MeQ 2 CY"NN-OMeI R No. R 3 Phys. data

IR)

1 H 2 2-F 3 3-F 4 4-F 2-cl 6 3-Cl 7 4-cl 8 2-Br 9 3-Br 4-Br 0 11 2-1 0 12 3- 13 4-1 14 2-CN 3-CN 16 4-CN 17 2-NO 2 is 3-N02 19 4-NO 2 2-Methyl 80- 84 0

C

721 3-Methyl 89- 92 0

C

22 4-Methyl 0 23 2-Ethyl 24 3-Ethyl 4-Ethyl 26 2-n-Propyl 27 3-n-Propyl 28 4-n-Propyl 29 2-iso-Propyl 3-iso-Propyl 31 4-iso-Propyl 32 2-n-flutyl 33 3-n-Butyl 34 4-ri-Butyl 2-'iso-Butyl 900280 0.Z. 0050/41690 Table 3 (contd.) Nc. R Phys. data

IR)

36 37 38 39 41 42 43 44 46 47 48 49 C2 51 52 CC 53 2 54 56 57 C 58 C 59 C 4 60 61 62 63 64 66 67 68 69 71 72 73 3-iso-BUtyl 4-i so-Butyl 2-s ec-Btity 1 3-sec-Butyl 4-sec-Butyl 2-tert Butyl 3-tert Buty 1 4-tert. -Butyl 2-n-Penty, 3-n-Pentyl 4-n-P enty I 2-n-Hexyl 3-n-Hexy 1 4-n-Hexyl 2-CyclIopropy 1 3-Cyclopropyl 4-Cyclopropyl 2-Cycl1ohexy I 3-Cyclohexyl 4-Cyclohexyl 2-Methoxy 3-Mothoxy 4-Methoxy 2-Et.h oxy 3-.Ethoxy 4-Ethoxy 2-n-Propoxy 3-n-Propoxy 4-n-Propoxy 2-i So-P ropoxy 3-Iso-P ropoxy 4-i so-Propoxy 2-tert Butoxy 3-tert ButQxy 4-tert Butoxy 2-CF 3 3-CF 3 4-CF 3 900280 0.Z. 0050/41690 Table 3 (contd.) No. R3Phys. data

IR)

74 2-Benzyl 3-Benzyl 76 4-Benzyl 77 2-[4-ChlorobenzylI 78 2-[4-Methoxy-benzyl) 79 4-Methoxy-3-benzyl 2-[2-Phenylethyl) 81 3-[2-Phenylethyl] 82 4-[2-Phenylethyl] 83 2-Benzyloxy 84 3-Benzyloxy 4-Benzyloxy 86 2-Phenoxy 87 3-Phenoxy 88 4-Phenoxy 819 2-Phenyl 9 3-Pheny 91 4-Phenyl 92 2-[3-Br, 4-Me-phenyl) 93 2-[4-Me-pheny1 I 94 t phenyl) ropyl-phenyl) 96 4-[4-Bromophenoxy] 4 97 2,3-F2 98 2,4-F 2 99 2, 5-F7 4 4 100 2,6-F 2 101 3,4-F 2 102 3,5-F 2 103 2,3-Cl 2 104 2,4-C1 2 105 2,5-cl 2 106 2,6-cl 2 107 3,4-cl 2 108 3,5-cl 2 109 2,5-Br 2 110 2-Cl, 4-Br III 2-cl, 112 2-F, 6-C1 900280 0.Z. 0050/41690 Table 3 (contd.) No.

R

Phys. data

IR)

113 114 115 116 117 118 119 120 121 122 123 124 0 125 0 126 127 128 0 129 130 131 132 133 134 0 135 0 136 137 138 00 139 140 141 142 143 0 ~~144 145 146 147 148 149 3-Cl, 6-Br 4-F, 2-F, 4-Cl 4-F, 2-F, 3-Cl 4-F, 2-Cl 2-Cl, 6-Me 3-Cl, 2-Me 3-Cl, 4-Me 3-Cl, 6-Me 4-Cl, 4-Cl, 6-Me 3-F, 4-Me 3-F, 6-Me 2-Cl, 2,6-Cl 2 3-Me 3-CN, 4-Me 2,3-Me 2 2, 4-Me2 2,5-Me 2 2,6-Me2 3,4-Me 2 3, 5-Me2 2, 4,6-Me 3 2, 6-(CF 3 )2 2,4-(CF 3 )2

-CF

3 2-F, 5-CF3 4-F, 3-CF3 2-Cl, 4-CF 3 2, 3-(OCH 3 )2 2, 4-(OCH 3 )2 2, 5-(OCH 3 )2 2, 6-(OCH 3 )2 3, 4-(OCH3)2 3, 5-(OCH- 3 2 9002180 17 O.Z. 0050/41690 TabW (contd.) No. R 3 Phys. data (rnp., IR) 150 2-OCH 3 3-CH3 151 2-0CH 3 4-CH3 152 2-OCH 3 5-CH 3 153 2-OCH 3 4-Cl 154 2-OCH3, 155 2-OCH3, 3,5-C1 2 156 2-OCH 3 3,6-C1 2 157 2,6-(0CH 3 2 3-cl 158 4-OCH 3 2-Cl 159 4-OCH 3 3-Cl 160 4-OCH 3 3-F 161 4-OCH 3 2-CH 3 0C 0 C C- C C 18 O.Z. 0050/41690 In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, i Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, SPodosphaera leucotricha in apples, SUncinula necator in vines, I Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, i Pseudocercosporella herpotrichoides in wheat and barley, S Pyricularia oryzae in rice, Phytophthora infestans potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi. Either the fungi themselves, or the plants, seed or materials to be protected against fungal attack, or the soil are treated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.

The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, 0 19 O.Z. 0050/41690 for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics xylene), chlorinated aromatics chlorobenzenes), paraffins crude oil fractions), alcohols methanol, butanol), ketones cyclohexanone), amines ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals kaolins, aluminas, talc and chalk) and ground synthetic minerals highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as ligninsulfite waste liquors and methylcellulose.

The fungicides generally contain from 0.1 to 95, and preferably from S to 90, wt% of active ingredient. The application rates are from 0.02 to 3 o° kg or more of active ingredient per hectare, depending on the type of S effect desired. The novel compounds may also be used for protecting materials, on Paecilomyces variotii. When the compounds are used for °o 20 treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally sufficient.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. A solution of 90 parts by weight of compound no. 20 (Table 3) and S Oo 10 parts by weight of N-methyl-a-pyrrolidone, which is suitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 5 (Table 80 parts .35 by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of I ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 6 (Table 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing this solution in water, an aqueous dispersion is obtained.

r 0.Z. 0050/41690 IV. An aqueous dispersion of 20 parts by weight of compound no. 20 (Table 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280 0 C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely distributing this solution in water, an aqueous dispersion is obtained.

V. A hammer-milled mixture of 80 parts by weight of compound no. (Table 3 parts by weight of the sodium salt of diisobutylnaphthalenea-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound no. 21 (Table 3) S and 97 parts by weight of particulate kaolin. The dust contains 3wt% of S" the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 20 (Table 92 parts by weight of powdered silica gel and 8 parts by weight of 'I"Z paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 21 (Table 10 parts of the sodium salt of a phenolsulfonic acid-ureaformaldehyde condensate, 2 parts of silica gel and 48 parts of water, S which dispersion can be further diluted.

oo IX. A stable oily dispersion of 20 parts by weight of compound no. (Table 2 paits by weight of the calcium salt of dodecylbenzenesulfonic So acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.

35 In these application forms, the agents according to the invention may also o. i be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun- -Icides frequently results in a greater fungicidal action spectrum.

21 O.Z. 0050/41690 Use examples The prior art active ingredient 2-(phenoxymethyl)-phenylglyoxylic acid methyl ester-0-methyloxime disclosed in EP 253,213 was used for comparison purposes.

Use Example 1 Action on Botrytis cinerea Paprika seedlings of the "Neusiedler Ideal Elite" Variety were sprayed, after 4 to 5 leaves were well developed, to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus Botrytis cinerea, and placed at o 22 to 24 0 C in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses Scovered the major portion of the leaves.

The results show that active ingredient no. 20 (Table employed as a 0.05wt% spray liquor, has a better fungicidal action than prior art comparative agent A Use Example 2 Action on Pyrenophora teres Barley seedlings of the "Igri" variety were sprayed to runoff at the 2-leaf stage with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 hours in a high-humidity climatic cabinet kept at 18 0 C. The plants were then cultivated for a further 5 days in the greenhouse at 20-22 0 C and a relative humidity of 70%. The extent of fungus spread was then determined.

The results show that active ingredients nos. 5, 6 and 20 from Table 2 and nos. 20 and 21 from Table 3, when applied as a 0.05% spray liquor, have a better fungicidal action than prior art comparative agent A

Claims

2. A e 1. A benzyl ketone of the formula I 0 C C X-0RZ R1 where x x is CHor N, 3 Y Y is 0 or NR 4 1 1 RI and R 2 are each H or Cl-C 4 -alkyl,A 4, R 3 is H, halogen, cyano, nitro, Cl-C 6 -alkyl, C 3 -C 6 -cycloalkyl, 4 Cl-C 6 -alkoxy, halo-Cl-C 2 -alkyl, aryl-Cl-C 2 -alkyl, aryl- Cl-C 2 -alkoxy, aryloxy or aryl, and the aryl groups in turn may be substituted by from one to three of the radicals halogen, cyano, nitro, Cl-C 6 -alkyl, Cl-C 6 -alkoxy or halo- Cl-C 2 -alkyl, 4 R is OH, Cl-C 6 -alkoxy or aryl-Cl-C 2 -alkoxy and R 5 is HI, methyl, halogen or methoxy. 23 0.Z. 0050/41690 2. A fungicidal agent containing an inert carrier and a fungicidally effective amount of a compound of the formula I 0 C C /X-0R 2 R1 where X is CH or N, Y is 0or NR 4 RI and R 2 are each H or Cl-C 4 -alkyl, R 3 is H, halogen, cyano, nitro, Cl-C 6 -alkyl, C3-C 6 -cYcloalkyl, Cl-C 6 -alkoxy, halo-Cl-C 2 -alkyl, aryl-Cl-C 2 alkyl, aryl- Cl-C 2 -alkoxy, aryloxy or aryl, and the aryl groups in turn may be substituted by from one to three of the radicals halogen, cyano, nitro, Cl-C 6 alkyl, Cl-C 6 -alkoxy or halo- R4 is OH, Cl-C 6 -alkoxy or aryl-Cl-C 2 -alkoxy and R 5 is H, methyl, halogen or methoxy. 24 o0.Z. 0050/41690
3. A process for combating fungi, wherein the fungi or the plants, seed, materials or areas threatened by fungus attack are treated with a fungicidally effective amount of a compound of the formula I Y -R C X-OR2 I o Ri where X is CH or N, 0 Y is O or NR4, R 1 and R 2 are each H or C 1 -C 4 -alkyl, R 3 is H, halogen, cyano, nitro, CI-Cg-alkyl, C 3 -C6-cycloalkyl, C 1 -C 6 -alkoxy, halo-Cl-C 2 -alkyl, aryl-Ci-C 2 -alkyl, aryl- C 1 -C 2 -alkoxy, aryloxy or aryl, and the aryl groups in turn may be substituted by from one to three of the radicals halogen, cyano, nitro, C 1 -C 6 -alkyl, C 1 -Cg-alkoxy or halo- Cl-C2-alkyl, R 4 is OH, Ct-C 6 -alkoxy or aryl-cl-c2-alkoxy and R 5 is H, methyl, halogen or methoxy.
4. A compound of the formula I as set forth in claim 1, where Ri and R 2 are methyl, Y is 0, K is CH and R 3 is hydrogen. A compound of the formula I as set forth in claim 1, where RI and R 2 are methyl, V is 0, X is N and RS is methyl in the 2-position. 6, A compound of the formula I as set forth in claim 1, where RI and R2 are methyl, Y is 0, X is CH and R 3 is methyl in the 2-position. DATED this 25th day of June 1991. BASF AKTIENGESELLSCHAFT WATEIMARK PATEr TRADEMARK ATT)RNEYS "THE ATRILM" 290 BURWXOD ROAD HAWTHORN. VIC. 3122.